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US5159027A - Stabilized polyphenylene ether resin and process for the preparation of the same - Google Patents

Stabilized polyphenylene ether resin and process for the preparation of the same Download PDF

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Publication number
US5159027A
US5159027A US07/400,120 US40012089A US5159027A US 5159027 A US5159027 A US 5159027A US 40012089 A US40012089 A US 40012089A US 5159027 A US5159027 A US 5159027A
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Prior art keywords
group
polyphenylene ether
resin
groups
hydrogen atom
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Inventor
Akihiro Kanayama
Sumio Ueda
Sadao Ibe
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Asahi Kasei Corp
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Asahi Kasei Kogyo KK
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Priority to US08/330,063 priority Critical patent/USRE35695E/en
Assigned to ASAHI KASEI KOGYO KABUSHIKI KAISHA reassignment ASAHI KASEI KOGYO KABUSHIKI KAISHA ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: IBE, SADAO, KANAYAMA, AKIHIRO, UEDA, SUMIO
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/48—Polymers modified by chemical after-treatment
    • C08G65/485—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C08L71/126—Polyphenylene oxides modified by chemical after-treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S525/905—Polyphenylene oxide

Definitions

  • the present invention relates to a novel polyphenylene ether resin and a process for the preparation of the same. More particularly, the present invention relates to a novel polyphenylene ether resin in which the polyphenylene ether chains resin collectively contain at least a specific amount of terminal 6-chroman groups and which has an improved resistance to thermal oxidative deterioration at the time of processing and at the time of use at high temperatures, and also to a process for the preparation of the same. Furthermore, the present invention relates to a composition comprising this novel polyphenylene ether resin and a polystyrene resin.
  • Polyphenylene ethers have excellent mechanical properties, electrical characteristics and heat resistance and, therefore, are widely used as thermoplastic molding materials.
  • polyphenylene ethers have, as well as these advantageous properties, a disadvantage in that they are likely to undergo thermal oxidative deterioration. Accordingly, their use is limited in the fields where they are likely to undergo thermal oxidative deterioration.
  • uses of various stabilizers, such as amines and organic phosphorus compounds have been proposed.
  • Another object of the present invention is to provide a process for preparing a polyphenylene ether resin having the above characteristics, which can easily be practiced.
  • Still another object of the present invention is to provide a composition comprising the above-mentioned polyphenylene ether resin and a polystyrene resin, which has excellent moldability as well as excellent resistance to thermal oxidative deterioration.
  • a polyphenylene ether resin comprising a plurality of polyphenylene ether chains, each comprising recurring phenylene ether units,
  • R 1 through R 5 each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, an aryl group or a substituted aryl group
  • R 6 through R 9 each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, a halogen atom, an aryl group, a substituted aryl group, an alkoxyl group, an N-lactam group, a carboxylic acid amide group, a carboxylic acid group, a carboxylic anhydride group, a carboxylic acid ester group, a nitrile group, an acyl group or an acyloxy group, with the proviso that R 6 and R 7 , and R 8 and R 9 are independently bonded
  • the amount of said terminal chroman groups is at least 0.01 in terms of the number of the terminal 6-chroman groups per 100 phenylene ether units in the resin, and the number average molecular weight of the resin is in the range of from 1,000 to 100,000.
  • the polyphenylene ether resin of the present invention comprises polyphenylene ether chains containing 6-chroman groups as terminal groups.
  • the number average molecular weight of the polyphenylene ether resin is within the range suitable for use as an engineering resin (about 10,000 to about 30,000), it is preferred that the number of the terminal 6-chroman groups be at least 0.15, especially at least 0.2, per 100 phenylene ether units.
  • the upper limit is not particularly critical, and the larger the amount of the terminal 6-chroman groups, the higher the resistance of the resin to thermal oxidative deterioration.
  • the polyphenylene ether chain of the polyphenylene ether resin of the present invention is defined as having phenylene ether units generally represented by ##STR6## as recurring units, and there is not any other particular limitation.
  • Representative examples of polyphenylene ether chains include those which are comprised of at least one type of phenylene ether units represented by the following formula (b): ##STR7## wherein R 1 through R 5 each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, an aryl group or a substituted aryl group.
  • These chains may further contain monomer units represented by formulae (h), (i) and (j) described hereinafter.
  • the alkyl group is an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms.
  • a halogen atom such as fluorine, chlorine or bromine
  • a hydroxyl group such as an amino group
  • a lower alkoxyl group such as an amino group, and a lower alkoxyl group.
  • R 1 be a lower alkyl group, such as a methyl, ethyl, propyl, isopropyl or n-butyl group, or a phenyl or naphthyl group, and that R 2 through R 5 are each independently a hydrogen atom or a lower alkyl group.
  • combinations of substituents include a combination in which R 1 is a methyl or phenyl group and each of R 2 through R 5 is a hydrogen atom, and a combination in which each of R 1 and R 2 is a methyl group and each of R 3 through R 5 is a hydrogen atom. It is particularly preferred that R 1 be a methyl group and each of R 2 through R 5 be a hydrogen atom, and phenylene ether units of this type be contained in an amount of 90 to 100%, based on the total phenylene ether units.
  • the monomer corresponding to the phenylene ether unit having the most preferred R 1 through R 5 satisfying these conditions there can be mentioned (i) 2,6-dimethylphenol, (ii) 2-methyl-6-phenylphenol and (iii) 2,3,6-trimethylphenol.
  • a homopolymer of monomer (i) or (ii) or a copolymer of monomer (i) with monomer (ii) and/or monomer (iii) is preferably used as the polyphenylene ether polymer as the essential skeleton of the resin of the present invention.
  • 63-301222 propose incorporation of 2-(dialkylaminomethyl)-6-methylphenylene ether units represented by the following formula (h): ##STR8## wherein R and R' each independently represent an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 22 carbon atoms, an acyloxyalkyl group having 3 to 22 carbon atoms or a polyalkylene ether group having 4 to 20 carbon atoms,
  • R represents an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 22 carbon atoms, an acyloxyalkyl group having 3 to 22 carbon atoms or a polyalkylene ether group having 4 to 20 carbon atoms and Ph represents a phenyl group.
  • the molecular weight of the polyphenylene ether resin of the present invention is 1,000 to 100,000 in terms of number average molecular weight.
  • the number average molecular weight of the resin is preferably in the range of from about 6,000 to about 60,000.
  • the number average molecular weight be about 10,000 to about 30,000.
  • the number average molecular weight referred to in the present invention is determined by gel permeation chromatography, using the calibration curve of standard polystyrene.
  • a plurality of polyphenylene ether chains collectively contain terminal 6-chroman groups represented by formula (a) in an amount of at least 0.01 in terms of the number of the terminal chroman groups per 100 phenylene ether units in the resin.
  • R 1 through R 5 are as defined for formula (b).
  • R 6 through R 9 each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, a halogen atom, an aryl group, a substituted aryl group, an alkoxy group, an N-lactam group, a carboxylic acid group, a carboxylic anhydride group, a carboxylic acid ester group, a carboxylic acid amide group, a nitrile group, an acyl group or an acyloxy group.
  • R 6 and R 7 , and R 8 and R 9 are independently bonded to form a ring, or are not bonded to each other.
  • the alkyl group is an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and a lower alkyl group is especially preferred.
  • a substituent of the substituted alkyl group there can be mentioned a halogen atom, such as fluorine, chlorine and bromine, a hydroxyl group, an amino group, and a lower alkoxyl group.
  • a lower alkenyl group such as an ethylenyl group or a 3-propenyl group is preferred as the alkenyl group.
  • a typical example of a substituted alkenyl group is a 1-hydroxyl-3-propenyl group.
  • the aryl group is an aryl group having 6 to 20 carbon atoms.
  • substituent of the substituted aryl group there can be mentioned a lower alkyl group, a lower alkoxyl group, a halogen atom, such as fluorine, chlorine and bromine, a hydroxyl group, an amino group, and an aminoalkyl group, such as an aminomethyl group.
  • aryl group means an aromatic ring group in a broad sense, and the aryl group includes not only an aryl group in a narrow sense but also a heterocyclic aromatic ring group, such as a pyridyl group or a triazyl group.
  • N-lactam groups include N-2-pyrrolidonyl and N- ⁇ -caprolactamoyl groups.
  • carboxylic acid amide groups include carbamoyl, phenylcarbamoyl and ceryl groups. Acetoxycarbonyl and benzoyloxycarbonyl groups are preferred as the carboxylic anhydride group.
  • carboxylic acid ester groups there can be mentioned methoxycarbonyl, ethoxycarbonyl and allyloxycarbonyl groups.
  • Acetyl and benzoyl groups can be mentioned as representative examples of acyl groups.
  • Acetoxy and benzoyloxy groups can be mentioned as preferred examples of acyloxy groups.
  • substituents R 6 through R 9 each be hydrogen atoms, and in this case, it is preferred that the remaining substituent(s) be selected from aryl groups, substituted aryl groups, carboxylic acid groups, carboxylic anhydride groups, carboxylic acid ester groups, carboxylic acid amide groups, nitrile groups and N-lactam groups. From the viewpoint of stability against thermal oxidative deterioration and also from the viewpoint of the preparation process described hereinafter, it is especially preferred that at least one of R 8 and R 9 be an aryl group or a substituted aryl group.
  • aryl groups or substituted aryl groups in the definition of R 6 through R 9 there can be mentioned phenyl, tolyl, chlorophenyl, naphthyl, 4-pyridyl and 3,5-diamino(s)-triazyl groups.
  • the amount of terminal 6-chroman groups can be determined by using the nuclear magnetic resonance spectrum.
  • the stabilized polyphenylene ether resin of the present invention has terminal 6-chroman groups (a), when the polyphenylene ether resin is melted, the resin shows excellent properties such that not only is formation of a rearrangement structure (g) much less than in the conventional polyphenylene ether resins but also the molecular weight is substantially not changed.
  • the present invention is different from the melting terminal capping process proposed in the specification of U.S. Pat. No. 4,760,118 (Japanese Patent Application Laid-Open Specification No. 63-295632) in that the rearrangement reaction per se is suppressed in the present invention. Therefore, not only formation of hydroxyl groups but also formation of a methylene group which is present between two benzene rings and activated by these benzene rings, is controlled.
  • the polyphenylene ether resin of the present invention is a molding material having excellent stability.
  • the number of phenolic hydroxyl groups be not greater than 0.5 per 100 phenylene ether units in the resin and the number of rearrangement structures of formula (g) (typically, a rearrangement structure of formula (e) which would be formed in the case of a resin comprised mainly of poly[oxy(2,6-dimethyl-1,4-phenylene)], which resin is commercially important) be not greater than 0.1 per 100 phenylene ether units in the resin.
  • the stabilized polyphenylene ether resin of the present invention is advantageous as a molding material in that not only do problems of plasticization and the like not occur, but also deterioration and increase of the viscosity by thermal oxidation in the melt molding are greatly suppressed, and in that a molded article which is improved in suppression of thermal oxidative deterioration which would occur during the use at high temperatures, can easily be obtained.
  • the stabilized polyphenylene ether resin of the present invention can be prepared according to the following process.
  • a process for the preparation of a stabilized polyphenylene ether resin as described above which comprises heating a phenylene ether polymer having terminal groups represented by the following formula (c): ##STR11## wherein R 1 through R 5 are as defined in formula (a), and R 10 and R 11 each independently represent a hydrogen atom, an alkyl group or a substituted alkyl group, with the proviso that R 10 and R 11 do not simultaneously represent a hydrogen atom,
  • the alkyl and substituted alkyl groups as R 10 and R 11 in formula (c) are preferably selected from alkyl groups having 1 to 20 carbon atoms, hydroxyalkyl groups having 1 to 20 carbon atoms, alkoxyalkyl groups having 2 to 22 carbon atoms, acyloxyalkyl groups having 3 to 22 carbon atoms, and polyalkylene ether groups having 4 to 20 carbon atoms.
  • a phenylene ether polymer having this terminal group (c) is obtained by subjecting a phenolic compound having at least one benzylic hydrogen at the ortho-position relative to the hydroxyl group to oxidative coupling polymerization or copolymerization in the presence of a catalyst comprising a primary or secondary amine (see, for example, the specification of U.S. Pat. No. 4,788,277).
  • the obtained polymer is a mixture of a phenylene ether polymer having a terminal group represented by formula (c) and a phenylene ether polymer having a terminal structure in which the primary or secondary amine is not bonded to the benzylic position.
  • this mixture can be used without being separated into the respective phenylene ether polymers.
  • the ratio between the former and latter phenylene ether polymers in the mixture is not particularly critical, but it is preferred that the ratio of the number of terminal groups of the former to the number of terminal groups of the latter be at least 0.4, especially at least 0.9.
  • the ratio of the unsaturated compound represented by general formula (d) to the phenylene ether polymer having terminal groups represented by formula (c) in the reaction of the present invention is preferably such that the amount of the unsaturated compound of formula (d) is about 2 to about 50 equivalents per equivalent of the phenylene ether polymer having terminal groups represented by formula (c).
  • terminal groups of formula (a) would probably be formed by Diels-Alder reaction between the unsaturated compound of formula (d) and an intermediate structure of the following formula (k): ##STR13## which is formed by the decomposition of the terminal groups of formula (c) when heated to a temperature of not lower than the glass transition temperature.
  • At least one of the substituents be an electron withdrawing group, such as a carbonyl group or a cyano group.
  • an unsaturated compound of formula (d) in which R 8 and/or R 9 are/is an aryl group or a substituted aryl group, as described hereinbefore.
  • unsaturated compounds (d) include styrene, ⁇ -methylstyrene, chlorostyrene, methylstyrene, stilbene, cinnamyl alcohol, benzalacetone, ethyl cinnamate, cinnamoyl nitrile, 4-vinylpyridine and 2-vinyl-3,5-diamino- (s)-triazine.
  • the orientation of the formed terminal group is likely to depend on the stability of the intermediate radical.
  • a structure having terminal groups of the type represented by formula (o) is likely to be formed: ##STR16##
  • Japanese Patent Publication No. 45-40551 and Japanese Patent Publication No. 46-32427 disclose processes in which a polyphenylene ether is reacted with styrene or a styrene derivative in the presence of a basic compound or Bronstead acid.
  • These prior techniques are suitably carried out, using a solution, at a temperature lower than 140° C., and are fundamentally different from the preparation process of the present invention which is suitably carried out in the molten state at a temperature of not lower than the glass transition temperature of the phenylene ether polymer.
  • terminal 6-chroman groups (a) are substantially not formed, so that the stabilized polyphenylene ether resin of the present invention cannot be prepared.
  • unsaturated compound free of an aromatic ring can also be used as unsaturated compound (d).
  • unsaturated compounds (d) of such a type include acrylic acid; acrylic acid esters, such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, isodecyl acrylate, lauryl acrylate, lauryltridecyl acrylate, tridecyl acrylate, cetylstearyl acrylate, stearyl acrylate, cyclohexyl acrylate and benzyl acrylate; acrylamide; acrylonitrile; methacrylic acid; methacrylic acid esters, such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, is
  • the phenylene ether polymer having terminal groups (c), which is used as the starting material for the stabilized polyphenylene ether resin of the present invention, is considered to be decomposed when melted, to thereby form an intermediate structure represented by the following formula (k): ##STR17## It has been found that the rate of this type of decomposition of the polyphenylene ether polymer at a temperature higher than about 200° C. is greatly different from the decomposition rate at a temperature lower than about 200° C.
  • terminal groups represented by the following formula (p): ##STR18## these terminal groups are substantially completely decomposed within several minutes when heated to 250° C., but these terminal groups are reduced only by half even after the lapse of 10 hours when heated to 180° C.
  • the phenylene ether polymer in the preparation of the stabilized polyphenylene ether resin of the present invention, for example, when a phenylene ether polymer having terminal groups of formula (p) as terminal groups (c) is used, it is preferred that the phenylene ether polymer be mechanically mixed with unsaturated compound (d) at a temperature lower than 180° C. prior to heating to a temperature of not lower than the glass transition temperature.
  • the mixing method is not particularly critical.
  • a method in which dry blending is carried out by using a Henschel mixer a method in which drying is carried out after blending, a method comprising dissolving unsaturated compound (d) in a solvent capable of dissolving unsaturated compound (d) but incapable of dissolving the polyphenylene ether, such as methanol or pentane to obtain a solution, impregnating a powdery polyphenylene ether polymer having terminal groups (c) with the solution and then removing the solvent by drying, a master batch method utilizing the above-mentioned methods, and a method in which a region maintained at a temperature lower than 180° C.
  • a phenylene ether polymer having terminal groups (c) and unsaturated compound (d) are fed to this region. After heating to a temperature higher than 180° C., the same or different type of unsaturated compound (d) can be additionally supplied.
  • the phenylene ether polymer having terminal groups (c) and unsaturated compound (d), which has been thus mechanically mixed, are heat-melted at a temperature of not lower than the glass transition temperature (about 208° C.) of the phenylene ether polymer. It is preferred that the heating temperature be higher by 20° to 150° C., especially by 50° to 120° C., than the glass transition temperature.
  • the suitable heating time varies according to the temperature and is not simply determined, but the heating is conducted for a time sufficient to complete the reaction. In general, it is sufficient to heat for about 1 minute to several minutes. Too long a heating time does not bring any significant additional effect. Since the rate of the reaction of forming terminal 6-chroman groups (a) is generally very high at a temperature of not lower than the glass transition temperature, application of excessive heat is not preferred.
  • the heating should be carried out in the absence of a radical polymerization initiator. Also oxygen should be purged as much as possible. Accordingly, it is preferred that a nitrogen gas atmosphere or the like be employed as the reaction atmosphere.
  • the polyphenylene ether resin of the present invention has high compatibility with a polystyrene resin, and when the polyphenylene ether resin of the present invention is blended with a polystyrene resin, a resin composition having improved resistance to thermal oxidative deterioration and a good moldability is obtained.
  • a resin composition comprising 1 to 99% by weight of the polyphenylene ether resin of the present invention and 1 to 99% by weight of a polystyrene resin.
  • Polystyrene resins often used together with polyphenylene ether resins which have been well-known to those skilled in the art, can be used as the polystyrene resin.
  • polystyrene resin for example, there can be mentioned styrene homopolymers, and copolymers of styrene with other ethylenically unsaturated monomers which are used in an amount not impairing the compatibility with the polyphenylene ether polymer.
  • these comonomers include ⁇ -methylstyrene, acrylonitrile, methacrylonitrile, acrylic acid esters, methacrylic acid esters, maleic anhydride, N-alkylmaleimides, N-arylmaleimides and vinyloxazoline.
  • a defect inherent in a polyphenylene ether resin that is, low impact resistance
  • improved resistance can be obtained.
  • high impact resistance polystyrene an ABS resin and an AES resin.
  • styrene/butadiene block copolymers and styrene/isoprene block copolymers can also be used. Also in this case, there can be obtained a composition which is much improved in stability to thermal oxidative deterioration as compared to conventional similar compositions.
  • the stabilized polyphenylene ether resin of the present invention can be blended with a polystyrene resin at any desired ratio.
  • the amount of the former can be 1 to 99% by weight, preferably 50 to 99% by weight.
  • the composition of the polyphenylene ether resin and a polystyrene resin can be formed during or after the preparation of the stabilized polyphenylene ether resin of the present invention.
  • a desired composition can be obtained by dry-blending a phenylene ether polymer having terminal groups (c), a polystyrene resin and an unsaturated compound of formula (d) and melt-kneading the resultant blend by means of a roll mill, a twin-screw extruder or the like.
  • the stabilized polyphenylene ether resin of the present invention or a composition comprising this resin and a polystyrene resin can advantageously be formed into a film, and the obtained film has very excellent characteristics.
  • the stabilized polyphenylene ether resin of the present invention or a composition comprising this stabilized polyphenylene ether resin and a polystyrene resin, and a film can be stably prepared therefrom.
  • the thickness of the film is not particularly critical, but the thickness is generally 5 to 1,000 ⁇ m and preferably 30 to 500 ⁇ m.
  • This film has not only excellent heat resistance, electrically insulating properties and mechanical properties but also improved resistance to thermal oxidative deterioration, and therefore, the film can be used as an insulating film and the like.
  • the process for the preparation of films is not particularly critical.
  • an ordinary melt-compression molding method and a T-die film-forming method in which the resin is heated in the extruder and is extruded from a flat die.
  • a solution-casting method also can be employed in which the stabilized polyphenylene ether resin is dissolved in an appropriate solvent, such as toluene, chloroform or tetrachloroethane, and a film can also be formed from the solution by using a film-forming machine.
  • Inorganic fillers such as glass fibers, various stabilizers, plasticizers, flame retardants, pigments and the like can be appropriately incorporated into the polyphenylene ether resin of the present invention in accordance with conventional techniques.
  • the viscosity of the polymer is measured at 30° C. with respect to a 0.5% chloroform solution by means of a Ubbellohde viscometer and is expressed in the unit of ⁇ sp/c .
  • GPC gel permeation chromatography
  • thermogravimetric weight decrease of the polymer is measured in air under conditions of 350° C. and 60 minutes with respect to a powder obtained by a method comprising forming a 5% by weight solution of a molded article in toluene, adding an equal amount of methanol to the solution to precipitate the polymer, recovering the polymer by filtration, washing the polymer with methanol and drying the polymer, and is expressed in terms of % by weight.
  • the resistance of the polymer to thermal oxidative deterioration is determined in the following manner.
  • a molded article is dissolved in chloroform, and a film (having a thickness of 50 to 60 ⁇ m) formed from the solution by a casting method is allowed to stand in an air-circulating oven maintained at 180° C. for 7 hours.
  • An increment of the absorbance at 1695 cm -1 is measured by means of an infrared spectrophotometer and is expressed as a relative value.
  • This absorbance is ascribed to an aldehyde group or carboxyl group formed by oxidation of the methyl groups of recurring units represented by the following formula (q): ##STR19## and the absorbance is an index for the degree of oxidative deterioration.
  • a starting phenylene ether polymer is prepared by oxidative coupling polymerization of 2,6-xylenol in the presence of dibutylamine according to the process disclosed in the specification of U.S. Pat. No. 4,788,277 (Japanese Patent Application No. 62-77570).
  • the viscosity of the obtained phenylene ether polymer is 0.545 and the glass transition temperature is about 208° C. From the results of the 1 H-nuclear magnetic resonance spectrum analysis, it is confirmed that terminal groups represented by the following formula (r): ##STR20## are present in an amount of 0.32 in terms of the number of the terminal groups per 100 main recurring units (q).
  • the obtained pellet is subjected to 1 H-nuclear magnetic resonance spectrum analysis. As a result, it is confirmed from the area value of a signal of 5.02 ppm that terminal groups represented by the following formula (s): ##STR21## are present in an amount of 0.25 in terms of the number of the terminal groups per 100 main recurring units (q), and from the area value of a signal of 3.86 ppm, it is confirmed that rearrangement structures of formula (e) are present in an amount of 0.03 in terms of the number of the rearrangement structures per 100 main recurring units (q).
  • free phenolic hydroxyl groups are present in an amount of 0.45 in terms of the number of free phenolic hydroxyl groups per 100 main recurring units (q).
  • the number average molecular weight determined by GPC is 24,500, and the viscosity is 0.547.
  • the pellet is molded at 330° C. by means of an injection molding machine (IS80EPN produced by Toshiba Kikai K.K., Japan) to form a test piece.
  • This test piece (a strip having a width of 6.4 mm) is analyzed in the same manner as described above. It is confirmed that terminal groups of formula (s) are present in an amount of 0.23 in terms of the number of the terminal groups per 100 main recurring units (q) and rearrangement structures of formula (e) are present in an amount of 0.13 in terms of the number of the rearrangement structures per 100 main recurring units (q). It also is confirmed that free phenolic hydroxyl groups are present in an amount of 0.69 in terms of the number of free phenolic hydroxyl groups per 100 main recurring units (q).
  • the number average molecular weight determined by GPC is 25,000, and the viscosity is 0.552.
  • the notched Izod impact strength of the test piece determined according to ASTM D-256, is 4 kg.cm/cm.
  • the results of the measurement of heat stability in air are shown in Table 1, together with the results obtained in Comparative Example 1.
  • Example 1 The same phenylene ether polymer having terminal groups (r), as used in Example 1, is extruded and pelletized under the same conditions as described in Example 1 except that styrene is not used. A test piece is prepared by subjecting this pellet to being injection-molded under the same conditions as described in Example 1. The results of the analysis of the pellet and test piece are collectively shown in Table 1.
  • Each of the amounts of the respective partial structures is expressed in terms of the number of the structures per 100 main recurring units (q), and the increment of the absorbance at 1695 cm -1 is a relative value.
  • the resin of Example 1 is excellent in stability of the injection-molded piece under a high temperature oxygen atmosphere and it is seen that the resin of Example 1 is an excellent molding material having high stability when used at high temperatures.
  • a pellet is prepared in the same manner as described in Example 1 except that ⁇ -methylstyrene is used instead of the styrene used in Example 1.
  • terminal groups of the following formula (t): ##STR22## are present in an amount of 0.20 in terms of the number of the terminal groups per 100 main recurring units (q)
  • rearrangement structures of formula (e) are present in an amount of 0.02 in terms of the number of the rearrangement structures per 100 main recurring units (e).
  • free phenolic hydroxyl groups are present in an amount of 0.48 in terms of the number of free phenolic hydroxyl groups per 100 main recurring units (q).
  • the number average molecular weight determined by GPC is 23,600, and the viscosity is 0.531.
  • a starting phenylene ether polymer is prepared by polymerizing 90 parts by weight of 2,6-dimethylphenol and 10 parts by weight of 2,3,6-trimethylphenol in the same manner as described in Example 1.
  • the viscosity of the obtained phenylene ether polymer is 0.568.
  • Terminal groups of formula (r), formula (u) and formula (v): ##STR23## are present in a total amount of 0.36 in terms of the number of these terminal groups per 100 phenylene ether units.
  • Free phenolic hydroxyl groups are present in an amount of 0.26 in terms of the number of free phenolic hydroxyl groups per 100 phenylene ether units.
  • Pellet of the stabilized polyphenylene ether resin of the present invention is obtained in the same manner as described in Example 1, using this phenylene ether polymer.
  • terminal groups of formula (s) and terminal groups of this type which are substituted with a methyl group at the 3- or 5-position are present in a total amount of 0.26 in terms of the number of these terminal groups per 100 phenylene ether units.
  • Rearrangement structures of formula (e) and structures of this type in which the hydrogens on the benzene ring are partly substituted with a methyl group are present in an amount of 0.03 per 100 phenylene ether units.
  • Free phenolic hydroxyl groups are present in an amount of 0.37 in terms of the number of free phenolic hydroxyl groups per 100 phenylene ether units.
  • the number average molecular weight determined by GPC is 27,300. ##STR24##
  • a starting phenylene ether polymer having a viscosity of 0.568 is prepared in the same manner as described in Example 1.
  • terminal groups (r) are present in an amount of 0.36 in terms of the number of the terminal groups per 100 units (q)
  • free phenolic hydroxyl groups are present in an amount of 0.25 in terms of the number of free phenolic hydroxyl groups per 100 units (q).
  • a starting phenylene ether polymer is prepared in the same manner as described in Example 1, except that the use of dibutylamine is omitted.
  • the viscosity of the obtained phenylene ether polymer is 0.574.
  • Terminal groups (r) are not present at all, and the number of free phenolic OH groups is 0.71 per 100 main recurring units (q).
  • Test pieces obtained in Example 14 and Comparative Examples 2 and 3 are melt and press-molded at 300° C. for 2 minutes to obtain films having a thickness of 50 to 60 ⁇ m.
  • the films are aged for 15 hours in an air-circulating oven at 180° C., and the degree of discoloration of each film is evaluated, based on the absorbance at 470 nm.
  • the obtained results are shown in Table 3.
  • Example 2 To 75 parts by weight of the stabilized polyphenylene ether resin pellet prepared in Example 1 are added to 25 parts by weight of impact resistance polystyrene (Styron 492 produced by Asahi Kasei Kogyo K.K., Japan), and they are sufficiently mixed, and melt-blended and pelletized at 300° C. by a twin-screw extruder. The obtained pellets are pressed at 300° C. for 3 minutes to obtain a film. The obtained film is exposed to heat at 150° C. for 7 hours, and the degree of advance of oxidative deterioration is evaluated, based on the absorption at 1695 cm -1 . The same pellets are injection-molded at 300° C. to form a test piece, and the test piece is exposed to heat under the same conditions as described above and the retention of Izod impact strength is measured. The results are shown in Table 4.
  • a film and a test piece are prepared in the same manner as described in Example 15 except that the polyphenylene ether resin pellet prepared in Comparative Example 1 is used.
  • the obtained film and test piece are exposed to heat at 150° C. for 7 hours, and the oxidative deterioration and the retention of impact strength are examined. The results are shown in Table 4.
  • the stabilized polyphenylene ether resin of the present invention has excellent thermal stability, differing from conventional polyphenylene ether resins which are likely to undergo thermal oxidative deterioration. Furthermore, a composition comprising this stabilized polyphenylene ether resin and a polystyrene resin has excellent thermal stability and moldability, and especially, a composition comprising the stabilized polyphenylene ether resin and a polystyrene resin containing a rubbery elastomer has not only excellent thermal stability but also improved impact resistance, overcoming another problem of the conventional polyphenylene ethers, i.e., poor impact resistance.

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US6156421A (en) * 1997-04-02 2000-12-05 Kimberly-Clark Worldwide, Inc. Stretched-filled microporous films and methods of making the same
US6211327B1 (en) 1999-02-05 2001-04-03 General Electric Company Process for the manufacture of low molecular weight polyphenylene ether resins
US6417274B1 (en) 1999-02-05 2002-07-09 General Electric Co. Process for the manufacture of functionalized polyphenylene ether resins
US20040225082A1 (en) * 2001-06-29 2004-11-11 Mutsumi Maeda Modified polyphenylene ether resin
US20070249766A1 (en) * 2006-04-19 2007-10-25 Asahi Kasei Chemicals Corporation Production process of polyphenylene ether composition
US20080081874A1 (en) * 2006-09-29 2008-04-03 Kim Balfour Poly(arylene ether) composition, method, and article
US20080081879A1 (en) * 2006-09-29 2008-04-03 Kim Balfour Crosslinked block copolymer composition and method
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US20080114102A1 (en) * 2006-11-13 2008-05-15 Balfour Kim G Poly(arylene ether)/polyolefin composition, method, and article
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US9187640B2 (en) 2011-06-20 2015-11-17 Asahi Kasei Chemicals Corporation Polyphenylene ether-based resin composition and method for producing the same
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US10080996B2 (en) 2014-05-01 2018-09-25 Sabic Global Technologies B.V. Skinned, asymmetric poly(phenylene ether) co-polymer membrane; gas separation unit, and preparation method thereof
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US10421046B2 (en) 2015-05-01 2019-09-24 Sabic Global Technologies B.V. Method for making porous asymmetric membranes and associated membranes and separation modules
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US6156421A (en) * 1997-04-02 2000-12-05 Kimberly-Clark Worldwide, Inc. Stretched-filled microporous films and methods of making the same
US6211327B1 (en) 1999-02-05 2001-04-03 General Electric Company Process for the manufacture of low molecular weight polyphenylene ether resins
US6303748B2 (en) 1999-02-05 2001-10-16 General Electric Company Process for the manufacture of low molecular weight polyphenylene ether resins
US6417274B1 (en) 1999-02-05 2002-07-09 General Electric Co. Process for the manufacture of functionalized polyphenylene ether resins
US6429277B1 (en) 1999-02-05 2002-08-06 General Electric Process for the manufacture of low molecular weight polyphenylene ether resins
US6437085B1 (en) 1999-02-05 2002-08-20 General Electric Company Process for the manufacture of low molecular weight polyphenylene ether resins
US20040225082A1 (en) * 2001-06-29 2004-11-11 Mutsumi Maeda Modified polyphenylene ether resin
US7645838B2 (en) 2001-06-29 2010-01-12 Asahi Kasei Kabushiki Kaisha Conjugated non-aromatic diene or dienophilic compound-modified polyphenylene ethers
US7544728B2 (en) 2006-04-19 2009-06-09 Asahi Kasei Chemicals Corporation Production process of polyphenylene ether composition
US20070249766A1 (en) * 2006-04-19 2007-10-25 Asahi Kasei Chemicals Corporation Production process of polyphenylene ether composition
US20080081874A1 (en) * 2006-09-29 2008-04-03 Kim Balfour Poly(arylene ether) composition, method, and article
US20080081879A1 (en) * 2006-09-29 2008-04-03 Kim Balfour Crosslinked block copolymer composition and method
US7718721B2 (en) 2006-11-13 2010-05-18 Sabic Innovative Plastics Ip B.V. Poly(arylene ether)/polyolefin composition, method, and article
US20080114102A1 (en) * 2006-11-13 2008-05-15 Balfour Kim G Poly(arylene ether)/polyolefin composition, method, and article
US20080113138A1 (en) * 2006-11-13 2008-05-15 William Eugene Pecak Poly(arylene ether)/polyolefin composition, method, and article
WO2012111628A1 (ja) 2011-02-14 2012-08-23 旭化成ケミカルズ株式会社 太陽光発電モジュール用接続構造体
US9231335B2 (en) 2011-02-14 2016-01-05 Asahi Kasei Chemicals Corporation Connection structure for solar power generation module
US9187640B2 (en) 2011-06-20 2015-11-17 Asahi Kasei Chemicals Corporation Polyphenylene ether-based resin composition and method for producing the same
DE112014003158B4 (de) 2013-07-05 2022-12-15 Asahi Kasei Chemicals Corporation Elektrisches Bauteil, umfassend ein Isolierharz-Formteil, sowie Verfahren zur Stabilisierung der Flammhemmung
US10080996B2 (en) 2014-05-01 2018-09-25 Sabic Global Technologies B.V. Skinned, asymmetric poly(phenylene ether) co-polymer membrane; gas separation unit, and preparation method thereof
US10207230B2 (en) 2014-05-01 2019-02-19 Sabic Global Technologies B.V. Composite membrane with support comprising poly(phenylene ether) and amphilphilic polymer; method of making; and separation module thereof
US10252220B2 (en) 2014-05-01 2019-04-09 Sabic Global Technologies B.V. Porous asymmetric polyphenylene ether membranes and associated separation modules and methods
US10252221B2 (en) 2014-05-01 2019-04-09 Sabic Global Technologies B.V. Porous asymmetric polyphenylene ether membranes and associated separation modules and methods
US10358517B2 (en) 2014-05-01 2019-07-23 Sabic Global Technologies B.V. Amphiphilic block copolymer; composition, membrane, and separation module thereof; and methods of making same
US10421046B2 (en) 2015-05-01 2019-09-24 Sabic Global Technologies B.V. Method for making porous asymmetric membranes and associated membranes and separation modules
US10307717B2 (en) 2016-03-29 2019-06-04 Sabic Global Technologies B.V. Porous membranes and associated separation modules and methods
US9815031B2 (en) 2016-03-29 2017-11-14 Sabic Global Technologies B.V. Porous membranes and associated separation modules and methods
DE102023133873A1 (de) 2022-12-05 2024-06-06 Asahi Kasei Kabushiki Kaisha Batteriehalter

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JP3109735B2 (ja) 2000-11-20
CN1029000C (zh) 1995-06-21
EP0407584A4 (en) 1992-08-05
EP0407584B1 (en) 1996-01-31
DE68925581D1 (de) 1996-03-14
WO1990008794A1 (fr) 1990-08-09
JP3052256B2 (ja) 2000-06-12
EP0407584A1 (en) 1991-01-16
CA1338545C (en) 1996-08-20
USRE35695E (en) 1997-12-16
DE68925581T2 (de) 1996-10-02
KR920010148B1 (ko) 1992-11-16
JPH02276823A (ja) 1990-11-13
KR910700289A (ko) 1991-03-14
CN1044471A (zh) 1990-08-08

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